CN104203827A

CN104203827A - Dispersed calcium carbonate containing material for improved stability under alkaline conditions

Info

Publication number: CN104203827A
Application number: CN201380017099.XA
Authority: CN
Inventors: 帕特里克·A·C·加纳; 丹尼尔·甘滕拜因
Original assignee: Omya Development AG
Current assignee: Omya Development AG
Priority date: 2012-03-30
Filing date: 2013-03-26
Publication date: 2014-12-10
Anticipated expiration: 2033-03-26
Also published as: PL2644568T3; CN104203827B; TW201338842A; RU2014143826A; WO2013144137A1; US20150040800A1; SI2644568T1; RU2591983C2; EP2830997B1; TWI586421B; ES2617571T3; DK2644568T3; LT2644568T; PT2644568T; CA2867000A1; EP2830997A1; EP2644568A1; IN2014MN01863A; HUE031954T2; HRP20170309T1

Abstract

The present invention relates to a method for preparing an aqueous calcium carbonate containing suspension, a suspension comprising a calcium carbonate containing material obtainable by the method as well as a calcium carbonate containing material obtainable by drying the suspension, and to the use of the suspension or calcium carbonate containing material in paper, paper coating, plastic and/or paint applications and to the use of the suspension for stabilizing the rheology of a sodium silicate and/or sodium hydroxide containing coating formulations for paper applications.

Description

The material calciferous under alkaline condition with the dispersion that improves stability

The present invention relates to a kind of method of preparing aqueous suspension calciferous, the suspensoid that comprises material calciferous that can obtain by described method, and the material calciferous that can obtain by dry described suspensoid, and relate to this suspensoid or the purposes of material calciferous in paper, paper coating, plastics and/or application of paints, also relate to this suspensoid purposes for the rheological of the stable coating formulation containing water glass and/or sodium hydroxide in paper application.

Mineral material and tackiness agent are as one of main ingredient of coating, paper and plastic material for the manufacture of multiple product.Wherein, mineral material has been contributed machinery and optical property as calcium carbonate and other particulate materials, and each component that tackiness agent (be generally latex base and be aqueous suspension or dispersion form) is the finished product to be produced provides required bounding force and cohesive force.

In this, problem be latex based adhesive by fossil resource as crude oil or similar resource is made and the therefore non-renewable fact.In addition, latex based adhesive conventionally provide quite low degradation property and therefore its for example the use in paper coating preparation can cause increasing environmental problem.

The method of the latex based adhesive in several suspensoids calciferous that can be used as coating formulation for reducing paper application has been proposed in the art.For example, a kind of method relates to interpolation water glass to reduce the binder levels in this coating formulation.In this, for example, with reference to EP 2 167324 B1, it relates to for lithographic printed sheet, it comprises at least one image receptive coating (image receiving coating) and optional one or more precoated layers (pre-coating) under described image receptive coating, described coating comprises pigment part, adhesive portion and optional additive, wherein pigment part is substantially by a kind of or compositions of mixtures that is selected from following fine particle pigment: carbonate, kaolin, solid or vacuolation (vacuolated) polymer pigment, wherein said adhesive portion comprises water glass.

Yet, described suspensoid calciferous and there is following shortcoming for the preparation of the method for this suspensoid: owing to adding water glass, the sodium ion that gained suspensoid has the pH of increase and comprises high density, caused the time dependent unstable of rheological, the Brookfield of suspensoid calciferous (Brookfield) viscosity increases considerably in time.Because viscosity increases, prepared suspensoid calciferous cannot be as the painting color preparation in paper application.

Therefore, for improving one's methods of suspensoid calciferous of preparation, have lasting demand, it has been processed above-mentioned technical problem and especially made can stablize the rheological of this composition under water glass and/or sodium hydroxide existence.

Therefore, an object of the present invention is to provide a kind of method for the preparation of suspensoid calciferous, described suspensoid has the latex based adhesive that at least content has reduced.Another object is to provide a kind of method for the preparation of suspensoid calciferous, and it stablizes the rheological temporal evolution that is characterized as of gained paper coating preparation.Another object is to provide a kind of method for the preparation of suspensoid calciferous, and it stablizes the rheological temporal evolution under water glass and/or sodium hydroxide existence that is characterized as of gained paper coating preparation.Another target is to provide a kind of method for the preparation of suspensoid calciferous that can carry out under the effective condition of cost, by reducing the content of the raw material that cost based on fossil resource is intensive or avoiding using this raw material.Another target can be from learning description of the invention below.

Theme aforementioned and that other objects limit by the present invention solves.

According to a first aspect of the invention, provide a kind of method for the preparation of aqueous suspension calciferous, wherein said method comprises the following steps:

A) provide the material calciferous of water-based filter cake (aqueous cake) or suspensoid form, its solids content is at least 45 % by weight of the gross weight based on water-based filter cake or suspensoid;

B) provide an alkali metal salt of at least one phosphonic acids, 0.01 % by weight to 5 % by weight that its amount is the gross dry weight based on material calciferous;

C) provide at least one phosphonic acids, 0.001 % by weight to 0.5 % by weight that its amount is the gross dry weight based on material calciferous;

D) make step material calciferous a) and step b) an alkali metal salt of at least one phosphonic acids contact, to obtain pH, be 10 to 14 suspensoid;

E) make steps d) suspensoid and step c) at least one phosphonic acids contact, to obtain pH, be 8 to 10 suspensoid; And

F) suspensoid grinding steps e optionally) obtaining.

The inventor finds unexpectedly, aforementioned the method according to this invention has caused not providing the suspensoid calciferous of latex based adhesive, thereby avoided using the cost intensive raw material based on fossil resource, and over time stable rheological and under water glass and/or sodium hydroxide exist stable rheological over time.Or rather, the inventor finds, the character of suspensoid calciferous can be added to limited phosphonic acids an alkali metal salt and the phosphonic acids under limited pH in this suspensoid and improve by follow-up.

Should be understood that for the purposes of the present invention, following term has following meaning:

For the purposes of the present invention, term " material calciferous " refers to the material that comprises the calcium carbonate based on material gross dry weight at least 50 % by weight calciferous.Term " calcium carbonate " refers to and grinds or natural whiting (GCC) in meaning of the present invention, and/or synthetic or precipitated chalk (PCC) and/or modified calcium carbonate (MCC).

Term " suspensoid " calciferous comprises insoluble solids and water and other optional additives in meaning of the present invention, and conventionally comprises a large amount of solids, therefore has more viscosity and generally than the liquid being formed by it, has higher density.

Term " acid " is interpreted as representative according to the acid of Bronsted (Bronsted) acid-alkali theory; That is to say the protophobe of acid for causing pH to reduce when being dissolved in the water.

Term " is dried " and is interpreted as material calciferous and has with respect to the weight of material calciferous the water that is less than by weight 0.3%.Water % measures according to Ka Er Fischer coulomb (Coulometric Karl Fischer) measuring method, wherein material calciferous is heated to 220 ℃, and measures the water-content that disengages and use nitrogen gas stream (100 ml/min) separation as steam in Ka Er Fischer coulomb unit.

Another aspect of the present invention refers to the suspensoid that comprises material calciferous that can obtain by the inventive method.Another aspect refers to the material calciferous that can obtain by dry described suspensoid.Another aspect of the present invention relates to suspensoid or the purposes of material calciferous in paper, paper coating, plastics and/or application of paints.Another aspect of the present invention relates to suspensoid for stablize the purposes of the rheological of coating formulation in paper application, and wherein said coating formulation comprises water glass and/or sodium hydroxide.

Define in the corresponding dependent claims the favourable embodiment of the present invention.

When below with reference to the present invention during for the preparation of the preferred embodiment of the method for aqueous suspension calciferous or ins and outs, should understand these preferred embodiments or ins and outs and also refer to suspensoid of the present invention, material calciferous of the present invention and purposes as defined herein, vice versa (as long as applicable).For example, if set the material calciferous of the inventive method, refer to grinding calcium carbonate, precipitated chalk, modified calcium carbonate or its mixture, the material calciferous of suspensoid of the present invention, the present invention's material calciferous and purposes also refer to grinding calcium carbonate, precipitated chalk, modified calcium carbonate or its mixture.

The present invention will and be described with reference to some accompanying drawing some special embodiments, but the present invention is not limited to this, and only be defined by the claims.Term except as otherwise noted, otherwise hereinafter described can be regarded as its conventional meaning conventionally.

When using in the specification and claims term " to comprise ", it does not get rid of other nonspecific elements of main or secondary function importance.For object of the present invention, term " by ... form " be considered to the preferred embodiment that term " comprises ".If hereinafter one group is defined as comprising at least embodiment of specific quantity, it also should be understood to disclose one group that preferably only these embodiments, consists of.

No matter when use term " to comprise " or " having ", these terms mean and are equivalent to " comprising " defined above.

While not having numeral-classifier compound to modify before noun, unless otherwise specifically indicated, otherwise it comprises singulative and plural form.

According to one embodiment of the invention, step material calciferous a) is grinding calcium carbonate, precipitated chalk, modified calcium carbonate or its mixture.

According to another embodiment of the invention, filter cake a) of step or the solids content of suspensoid are, 50 % by weight to 98 % by weight of the gross weight based on water-based filter cake or suspensoid, preferably 60 % by weight to 90 % by weight and more preferably 70 % by weight to 85 % by weight.

According to another embodiment of the present invention, the weight median particle d of step material calciferous a) ₅₀be 1 μ m to 100 μ m, preferred 1 μ m to 70 μ m, more preferably 1 μ m to 50 μ m, even more preferably 1 μ m to 25 μ m and most preferably 1 μ m to 10 μ m.

The basic metal of an alkali metal salt of at least one phosphonic acids according to one embodiment of the invention, step b) is selected from sodium, potassium, lithium and composition thereof, preferably, step b) the basic metal of an alkali metal salt of at least one phosphonic acids be sodium.

An alkali metal salt of at least one phosphonic acids according to another embodiment of the invention, step b) is selected from an alkali metal salt of di 2 ethylhexyl phosphonic acid and an alkali metal salt of tri methylene phosphonic acid, and preferably, an alkali metal salt of at least one phosphonic acids is an alkali metal salt of di 2 ethylhexyl phosphonic acid.

According to another embodiment of the present invention, the an alkali metal salt of at least one phosphonic acids step b) is an alkali metal salt of di 2 ethylhexyl phosphonic acid, it is selected from 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid (HEDP), methylenediphosphonate (MDP) (MDP), hydroxy methylene di 2 ethylhexyl phosphonic acid (HMDP), hydroxyl ring methylenediphosphonate (MDP) (HCMDP) and 1-hydroxyl-3-aminopropane-1,1-di 2 ethylhexyl phosphonic acid (APD), preferred 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid (HEDP).

An alkali metal salt of di 2 ethylhexyl phosphonic acid according to one embodiment of the invention, step b) is selected from (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid four sodium (Na ₄hEDP), (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid trisodium (Na ₃hEDP), (1-hydroxy ethylene) Disodium alendronate (Na ₂hEDP), (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid four potassium (K ₄hEDP), (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid tripotassium (K ₃hEDP) and (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid dipotassium (K ₂the metal-salt of di 2 ethylhexyl phosphonic acid HEDP), preferably, step b) is (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid four sodium (Na ₄hEDP).

According to another embodiment of the invention, the basic metal of at least one phosphonic acids step b) is the form of the aqueous solution, the aqueous solution that preferably comprises an alkali metal salt of at least one phosphonic acids, the amount of an alkali metal salt of described at least one phosphonic acids is 10 % by weight to 80 % by weight of the gross weight based on solution, preferably 20 % by weight to 66 % by weight and most preferably 30 % by weight to 50 % by weight.

According to another embodiment of the present invention, step c) at least one phosphonic acids be selected from di 2 ethylhexyl phosphonic acid and tri methylene phosphonic acid, preferably, step c) at least one phosphonic acids be di 2 ethylhexyl phosphonic acid.

According to one embodiment of the invention, step c) at least one phosphonic acids is to be selected from following di 2 ethylhexyl phosphonic acid: 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid (HEDP), methylenediphosphonate (MDP) (MDP), hydroxy methylene di 2 ethylhexyl phosphonic acid (HMDP), hydroxyl ring methylenediphosphonate (MDP) (HCMDP) and 1-hydroxyl-3-aminopropane-1,1-di 2 ethylhexyl phosphonic acid (APD), preferably, step c) at least one phosphonic acids is 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid (HEDP).

According to another embodiment of the invention, step c) form that at least one phosphonic acids is the aqueous solution, preferably comprise at least one phosphine aqueous acid, the amount of described phosphonic acids is 25 % by weight to 75 % by weight of the gross weight based on solution, preferably 35 % by weight to 65 % by weight and most preferably 45 % by weight to 60 % by weight.

According to another embodiment of the present invention, step b) an alkali metal salt of at least one phosphonic acids be 1-hydroxyl ethane 1, the sodium salt (Na of 1-di 2 ethylhexyl phosphonic acid ₄hEDP), and step c at least one phosphonic acids) is 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid (HEDP).

According to one embodiment of the invention, carry out steps d), wherein by step b) an alkali metal salt of at least one phosphonic acids add in step material calciferous a), the amount of described an alkali metal salt is 0.05 % by weight to 2.5 % by weight of the gross weight based on material calciferous, preferably its amount is 0.05 % by weight to 1.5 % by weight, more preferably its amount be 0.05 % by weight to 1 % by weight and most preferably its amount be 0.1 % by weight to 1 % by weight.

The pH of the suspensoid according to another embodiment of the invention, steps d) obtaining is 9 to 12, preferably 10 to 12 and most preferably from about 11.

According to another embodiment of the present invention, water is by steps d) suspensoid that obtains is diluted to solids content for 40 % by weight to 90 % by weight of the gross weight based on suspensoid, preferably 50 % by weight to 80 % by weight and more preferably 60 % by weight to 75 % by weight.

According to one embodiment of the invention, the solids content of suspensoid steps d) obtaining is 50 % by weight to 88 % by weight of the gross weight based on suspensoid, preferred 55 % by weight to 88 % by weight, more preferably 65 % by weight to 86 % by weight, even more preferably 68 % by weight to 84 % by weight and most preferably 72 % by weight to 82 % by weight.

According to another embodiment of the invention, the brookfield viscosity of suspensoid steps d) obtaining is 50mPas to 5000mPas at 23 ℃, at 23 ℃, be preferably 60mPas to 3000mPas, at 23 ℃, be more preferably 100mPas to 1000mPas and most preferably at 23 ℃ for 150mPas to 900mPas.

According to another embodiment of the present invention, carry out step e), wherein by step c) at least one phosphonic acids add steps d to) in the suspensoid that obtains, the amount of described phosphonic acids is 0.01 % by weight to 0.5 % by weight of the gross dry weight based on material calciferous, preferably its amount is 0.05 % by weight to 0.4 % by weight, more preferably its amount be 0.075 % by weight to 0.3 % by weight and most preferably its amount be 0.075 % by weight to 0.2 % by weight.

The pH of the suspensoid according to one embodiment of the invention, step e) obtaining is 9 to 10 and most preferably from about 9.4.

According to another embodiment of the invention, the brookfield viscosity of suspensoid step e) obtaining is 10mPas to 4900mPas at 23 ℃, at 23 ℃, be preferably 40mPas to 3000mPas, at 23 ℃, be more preferably 70mPas to 1000mPas and most preferably at 23 ℃ for 100mPas to 800mPas.

According to another embodiment of the present invention, at step e) carry out afterwards grinding steps f).

According to one embodiment of the invention, at 10 ℃ to 110 ℃, preferably 20 ℃ to 90 ℃ and most preferably at the temperature of 20 ℃ to 70 ℃, carry out grinding steps f).

According to another embodiment of the invention, carry out grinding steps f) until particle diameter is less than 50 % by weight to 98 % by weight that the mark of the material calciferous of 2 μ m is the gross weight based on material calciferous, preferred 60 % by weight to 98 % by weight, more preferably 70 % by weight to 98 % by weight and most preferably 75 % by weight to 98 % by weight.

According to another embodiment of the present invention, the brookfield viscosity of suspensoid step f) obtaining is 1mPas to 5000mPas at 23 ℃, at 23 ℃, be preferably 10mPas to 4000mPas, more preferably 20mPas to 3000mPas and 30mPas to 1000mPas at 23 ℃ most preferably at 23 ℃.

According to one embodiment of the invention, described method also comprises the concentrated step g of suspensoid that makes gained comprise material calciferous), make at least 60 % by weight that the solids content in suspensoid is the gross weight based on suspensoid, preferred 60 % by weight to 88 % by weight, more preferably 65 % by weight to 86 % by weight, even more preferably 70 % by weight to 84 % by weight and most preferably 75 % by weight to 82 % by weight.

According to another embodiment of the invention, at step f) carry out afterwards enrichment step g).

According to another embodiment of the present invention, described method also comprises step h), it makes step f) and/or step g) in the suspensoid that comprises material calciferous that obtains contact with water glass and/or sodium hydroxide.

According to one embodiment of the invention, carry out step h) contact, the water glass wherein adding and/or the amount of sodium hydroxide are that the gross dry weight based on material calciferous is greater than 0.001 % by weight, preferred 0.01 % by weight to 10 % by weight, more preferably 0.05 % by weight to 5 % by weight and most preferably 0.1 % by weight to 4 % by weight.

As mentioned above, the present invention for the preparation of the method for aqueous suspension calciferous comprise step a), b), c), d), e) and f).Hereinafter, will relate to the present invention further details, especially the present invention for the preparation of the abovementioned steps of the method for aqueous suspension calciferous.

step is a): material calciferous is provided

According to the present invention, for the preparation of the step of the method for aqueous suspension calciferous a), provide the material calciferous of water-based filter cake or suspensoid form, its solids content is at least 45 % by weight of the gross weight based on water-based filter cake or suspensoid.

According to one embodiment of the invention, material calciferous is grinding calcium carbonate, precipitated chalk, modified calcium carbonate or its mixture.

In meaning of the present invention, " grinding calcium carbonate " is (GCC) calcium carbonate that is obtained from natural origin, for example Wingdale, marble, calcite, chalk or rhombspar, and through wet type and/or dry process processing, for example grind, screen and/or separation, for example, by cyclonic separator or grading machine.

The feature of grinding calcium carbonate (GCC) can be the one or more of of for example marble, Wingdale, chalk and/or rhombspar.According to one embodiment of the invention, GCC obtains by dry grinding.According to another embodiment of the invention, GCC is by wet grinding and follow-up dry acquisition.

Usually, grinding steps can carry out with any conventional milling apparatus, for example, refinement is mainly carried out under the condition from the impact of auxiliary body (secondary body), at ball mill, rod mill, oscillating mill, crushing rolls, centrifugal impact mill, vertical ball mill, masher, needle mill, hammer mill, pulverizer, shredding machine, go to carry out in piece machine (de-clumper), cutting machine or other this equipment known to the skilled one or more of.In the situation that the material calciferous that material calciferous comprises wet grinding, grinding steps can make to occur under the condition of automatic grinding and/or undertaken by horizontal ball milling and/or additive method known to the skilled.The thus obtained material calciferous through wet type processing grinding can be washed and be dewatered by known method, for example, by flocculation, filtration or before being dried, force evaporation to carry out.Follow-up drying step can carry out with one step, and for example spraying is dry, or carries out with at least two steps.Also commonly, make this calcium carbonate material experience selected step (for example, flotation, bleaching or magnetic separation step) with removal of impurity.

In meaning of the present invention, " precipitated chalk " is (PCC) synthetic materials, and it precipitates after generally reacting in aqueous environments with lime by carbonic acid gas, or is precipitated and obtain in water by calcium and carbanion source.PCC can be vaterite, calcite or aragonite.

The feature of precipitated chalk (PCC) can be one or more of for example aragonite, vaterite and/or calcite mineral crystalline form.Aragonite is generally needle-like form, and vaterite belongs to hexagonal system.Calcite can form scalenohedron, prism-shaped, spherical and rhombohedron form.PCC can be prepared by different way, and for example, by precipitating with carbonic acid gas, soda lime process (lime soda process) or Suhl be (Solvay) method not, and wherein PCC is for producing the by product of ammonia.Gained PCC slurry can carry out mechanical dehydration and dry.

In meaning of the present invention, " modified calcium carbonate " feature (MCC) can be natural ground or the precipitated chalk with internal structure modification or surface reaction product.According to a preferred embodiment of the invention, modified calcium carbonate is the calcium carbonate of surface reaction.This modified calcium carbonate is for example known by WO 2000/039222 A1.

Preferably at least one material calciferous comprises grinding calcium carbonate (GCC).

In a preferred embodiment of the invention, the mixture that material calciferous comprises grinding calcium carbonate and precipitated chalk or modified calcium carbonate.

Except calcium carbonate, material calciferous can also comprise metal oxide (for example titanium dioxide and/or alchlor), metal hydroxides (as three aluminium hydroxides), metal-salt is (as vitriol, silicate, as talcum and/or kaolin clay and/or mica), carbonate (as magnesiumcarbonate and/or gypsum), stain white and composition thereof.

According to one embodiment of the invention, in material calciferous, calcium carbonate quantity is at least 80 % by weight of the gross dry weight based on material calciferous, for example at least 95 % by weight, preferably 97 % by weight to 100 % by weight, more preferably 98.5 % by weight to 99.95 % by weight.

Specific requirement of the present invention is that the solids content of filter cake or suspensoid is at least 45 % by weight of the gross weight based on water-based filter cake or suspensoid.

According to one embodiment of the invention, the solids content of filter cake or suspensoid is 50 % by weight to 98 % by weight of the gross weight based on water-based filter cake or suspensoid, preferably 60 % by weight to 90 % by weight and more preferably 70 % by weight to 85 % by weight.

The in the situation that of aqueous suspension, as what measured according to the method being provided in embodiment chapters and sections below, solids content can be 50 % by weight to 98 % by weight of the gross weight based on suspensoid, but be preferably 50 % by weight to 98 % by weight or 60 % by weight to 90 % by weight, and 70 % by weight to 85 % by weight more preferably.

The in the situation that of filter cake, the gross weight of solids content based on filter cake is generally 50 % by weight to 98 % by weight, preferably 60 % by weight to 90 % by weight and even more preferably 70 % by weight to 85 % by weight.

Described suspensoid can be by the material calciferous providing with powder type being provided form.

Should be understood that aqueous suspension that filter cake refers at least one material calciferous after filtration, centrifugal after or the cake that forms on filtration medium after sedimentation and decant.

In a preferred embodiment, the pH of described suspensoid or filter cake between 7 and 10, more preferably pH be 7 to 9 and most preferably pH be 8 to 9.

According to one embodiment of the invention, as measured by Sedigraph 5120, the weight median particle d of material calciferous ₅₀be 1 μ m to 100 μ m, preferred 1 μ m to 70 μ m, more preferably 1 μ m to 50 μ m, even more preferably 1 μ m to 25 μ m and most preferably 1 μ m to 10 μ m.For example, as measured by Sedigraph 5120, the weight median particle d of material calciferous ₅₀be 2 μ m to 9 μ m or 4 μ m to 9 μ m.

Run through presents, " particle diameter " of material calciferous is by describing by its size distribution.D _xthe value representation by weight particle of x% has the d of being less than _xthe corresponding diameter of diameter.This means d ₂₀20 % by weight that value is all particles are less than the particle diameter of this particle diameter, and d ₇₅75 % by weight that value is all particles are less than the particle diameter of this particle diameter.So d ₅₀value is weight median particle, and 50 % by weight of all particles are greater than or less than this particle diameter.Except as otherwise noted, otherwise for the purposes of the present invention, particle diameter is expressed as weight median particle d ₅₀.For gravimetry intermediate value grain particle diameter d ₅₀value, can be used the Sedigraph 5120 of the Micromeritics of u s company to install.At 0.1 % by weight Na ₄p ₂o ₇in the aqueous solution, measure.Use homogenizer and supersound process dispersed sample.

Step described aqueous suspension or filter cake a) preferably comprises, and the gross dry weight based on material calciferous is less than the polyacrylate based dispersion agent of 0.2 % by weight as the salt of polyacrylic ester.In a preferred embodiment of the invention, aqueous suspension a) of step or filter cake be not containing the dispersion agent of polyacrylate based as the salt of polyacrylic ester.

If step aqueous suspension or filter cake a) comprises polyacrylate based dispersion agent, described dispersion agent is selected from acrylate copolymer, vinylformic acid and ethylene copolymer and composition thereof excellently.The dispersion agent with a plurality of acidic sites can partly or entirely be neutralized as acrylate copolymer, vinylformic acid and ethylene copolymer and composition thereof.In a preferred embodiment, the neutralizing agent of the ion that use comprises basic metal and/or alkaline-earth metal, dispersion agent used according to the invention is partly or entirely neutralized, preferably neutralize 5% to 100% degree, more preferably neutralize 25% to 100% degree and most preferably neutralize 75% to 100% degree.In an especially preferred embodiment, the acidic site of dispersion agent is used the neutralizing agent that only contains sodium to neutralize.In another especially preferred embodiment, the acidic site of dispersion agent is used the neutralizing agent that only contains potassium to neutralize.In another especially preferred embodiment, the acidic site of dispersion agent is used the neutralizing agent containing the mixture of sodium and potassium to neutralize.

In another preferred embodiment, the acidic site of dispersion agent is partly or entirely neutralized by contained alkaline-earth metal ions in calcium carbonate water-based suspensoid, and for example, the reaction in－situ by the particle in organic dispersing agent and suspensoid neutralizes; Being about to dispersion agent adds in described suspensoid and in being added to calcium carbonate water-based suspensoid and is partly or entirely neutralized afterwards with the dispersion agent form not being neutralized of correspondence.In this case, the acidic site of dispersion agent is partly or entirely neutralized by alkaline-earth metal ions, preferably to 5% to 100% degree, more preferably to 25% to 100% degree and optimum 75% to 100% the degree of choosing.In a preferred embodiment, the acidic site of dispersion agent is partly or entirely neutralized by calcium ion and/or magnesium ion.

The molecular weight of such dispersion agent can be preferably between 1000g/mol and 100000g/mol, preferably between 2000g/mol and 40000g/mol, more preferably between 3000g/mol and 35000g/mol.Especially, if the neutralizing agent of the involved alkalimetal ion of acidic site of dispersion agent partly or entirely neutralizes, the molecular weight of this dispersion agent is preferably between 1000g/mol and 100000g/mol, more preferably between 2000g/mol and 40000g/mol and most preferably between 3000g/mol and 35000g/mol.In the situation that the partly or entirely neutralization of the neutralizing agent of the involved alkaline-earth metal ions of acidic site of dispersion agent, the molecular weight of this dispersion agent is preferably between 3000g/mol and 20000g/mol.

step b): an alkali metal salt that at least one phosphonic acids is provided

According to the step b of the inventive method), an alkali metal salt of at least one phosphonic acids is provided.An alkali metal salt of described at least one phosphonic acids provides with the amount of gross dry weight 0.01 % by weight to 5 % by weight based on material calciferous.

In a preferred embodiment, the an alkali metal salt of at least one phosphonic acids is with the amount of 0.05 % by weight to 2.5 % by weight of the gross dry weight based on material calciferous, the preferred amount of 0.05 % by weight to 1.5 % by weight, more preferably the amount of 0.05 % by weight to 1 % by weight and most preferably the amount of 0.1 % by weight to 1 % by weight provide.

Preferably, an alkali metal salt of described at least one phosphonic acids provides with the form of the aqueous solution.Preferably, the pH of the aqueous solution of an alkali metal salt that comprises at least one phosphonic acids is 10 to 14, more preferably 10 to 13 and most preferably 11 to 13.

If an alkali metal salt of at least one phosphonic acids provides with the form of the aqueous solution, the an alkali metal salt of at least one phosphonic acids that the described aqueous solution comprises following amount: 10 % by weight to 80 % by weight of the gross weight based on solution, are preferably 20 % by weight to 66 % by weight and most preferably are 30 % by weight to 50 % by weight.

The basic metal of an alkali metal salt of at least one phosphonic acids comprises the first family element of periodictable system.Therefore, the basic metal of an alkali metal salt of at least one phosphonic acids generally can be selected from lithium, sodium, potassium, rubidium, caesium, francium and composition thereof.

In a preferred embodiment of the invention, the basic metal of an alkali metal salt of at least one phosphonic acids is selected from sodium, potassium, lithium and composition thereof.The basic metal of an alkali metal salt of at least one phosphonic acids for example, step b) is sodium.The basic metal of an alkali metal salt of at least one phosphonic acids alternately, step b) is potassium.

An alkali metal salt of phosphonic acids is preferably an alkali metal salt of di 2 ethylhexyl phosphonic acid or an alkali metal salt of tri methylene phosphonic acid.For example, an alkali metal salt of phosphonic acids is preferably an alkali metal salt of di 2 ethylhexyl phosphonic acid.

Preferably, an alkali metal salt that an alkali metal salt of di 2 ethylhexyl phosphonic acid is Alkyl diphosphonate, for example 1-hydroxyl ethane 1, an alkali metal salt of 1-di 2 ethylhexyl phosphonic acid (HEDP).

An alkali metal salt that can be used for other di 2 ethylhexyl phosphonic acids of the present invention comprises an alkali metal salt of an alkali metal salt of methylenediphosphonate (MDP) (MDP), hydroxy methylene di 2 ethylhexyl phosphonic acid (HMDP), an alkali metal salt of hydroxyl ring methylenediphosphonate (MDP) (HCMDP) or 1-hydroxyl-3-aminopropane-1, an alkali metal salt of 1-di 2 ethylhexyl phosphonic acid (APD).

Preferably, an alkali metal salt of phosphonic acids is 1-hydroxyl ethane 1, an alkali metal salt of 1-di 2 ethylhexyl phosphonic acid (HEDP).

If an alkali metal salt that an alkali metal salt of phosphonic acids is tri methylene phosphonic acid, an alkali metal salt of described tri methylene phosphonic acid can be amino three (methylene phosphonic acid) an alkali metal salt (ATMP).

Described phosphonic acids an alkali metal salt also can comprise the phosphonyl group of comparatively high amts, for example diethylene triamine penta(methylene phosphonic acid) (DTPMP).

Described phosphonic acids an alkali metal salt also can comprise other group, as hydroxy-acid group.The example of an alkali metal salt of this phosphonic acids is phosphonosuccinic acid (phosphonosuccinic acid, PSA).

In a preferred embodiment of the invention, an alkali metal salt of di 2 ethylhexyl phosphonic acid is selected from (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid four sodium (Na ₄hEDP), (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid trisodium (Na ₃hEDP) and (1-hydroxy ethylene) Disodium alendronate (Na ₂hEDP).Alternately, an alkali metal salt of di 2 ethylhexyl phosphonic acid is selected from (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid four potassium (K ₄hEDP), (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid tripotassium (K ₃hEDP) and (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid dipotassium (K ₂hEDP).

For example, an alkali metal salt of di 2 ethylhexyl phosphonic acid is selected from (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid four sodium (Na ₄hEDP) and (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid four potassium (K ₄hEDP).Preferably, an alkali metal salt of di 2 ethylhexyl phosphonic acid is (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid four sodium (Na ₄hEDP).

step c): at least one phosphonic acids is provided

According to the step c of the inventive method), at least one phosphonic acids is provided.Described at least one phosphonic acids provides with the amount of 0.001 % by weight to 0.5 % by weight of the gross dry weight based on material calciferous.

In a preferred embodiment, at least one phosphonic acids is with the amount of gross dry weight 0.01 % by weight to 0.5 % by weight based on material calciferous, the preferred amount of 0.05 % by weight to 0.4 % by weight, more preferably the amount of 0.075 % by weight to 0.3 % by weight and most preferably the amount of 0.075 % by weight to 0.2 % by weight provide.

Preferably, described at least one phosphonic acids provides with the form of the aqueous solution.Preferably, the pH of the aqueous solution that comprises at least one phosphonic acids is 0 to 5, more preferably 0.5 to 4.5 and most preferably 1 to 4.

If at least one phosphonic acids provides with the form of the aqueous solution, at least one phosphonic acids that the described aqueous solution comprises following amount: its gross weight based on solution is preferably 25 % by weight to 75 % by weight, preferably 35 % by weight to 65 % by weight and most preferably 45 % by weight to 60 % by weight.

At least one phosphonic acids is preferably selected from di 2 ethylhexyl phosphonic acid and tri methylene phosphonic acid.For example, at least one phosphonic acids is preferably di 2 ethylhexyl phosphonic acid.

Preferably, at least one di 2 ethylhexyl phosphonic acid is Alkyl diphosphonate, and for example 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid (HEDP).

Can be used for other di 2 ethylhexyl phosphonic acids of the present invention and comprise methylenediphosphonate (MDP) (MDP), hydroxy methylene di 2 ethylhexyl phosphonic acid (HMDP), hydroxyl ring methylenediphosphonate (MDP) (HCMDP) or 1-hydroxyl-3-aminopropane-1,1-di 2 ethylhexyl phosphonic acid (APD).

If at least one phosphonic acids is tri methylene phosphonic acid, described tri methylene phosphonic acid can be amino three (methylene phosphonic acids) (ATMP).

Described at least one phosphonic acids also can comprise the phosphonyl group of comparatively high amts, as diethylene triamine penta(methylene phosphonic acid) (DTPMP).

Described at least one phosphonic acids also can comprise other group, as hydroxy-acid group.The example of an alkali metal salt of this phosphonic acids is phosphonosuccinic acid (PSA).

Preferably, at least one phosphonic acids is 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid (HEDP).

steps d): material calciferous is contacted with an alkali metal salt of at least one phosphonic acids

According to the steps d of the inventive method), make step material calciferous a) and step b) an alkali metal salt of at least one phosphonic acids contact.Carry out described contact so that acquisition pH is 10 to 14 suspensoid.

The pH of the aqueous suspension calciferous in a preferred embodiment of the invention, steps d) obtaining is 9 to 12, preferably 10 to 12 and more preferably from about 11.

Should be understood that selective basis step b of the present invention) the amount of an alkali metal salt of at least one phosphonic acids, make its in step material calciferous a) for enough, i.e. steps d) pH of the suspensoid calciferous that obtains is 10 to 14.

In order to fall into described steps d) final suspensoid pH scope, by step b) an alkali metal salt of at least one phosphonic acids add step to a) in material calciferous, the amount of interpolation is 0.01 % by weight to 5 % by weight of the gross dry weight based on material calciferous.

For example, by step b) an alkali metal salt of at least one phosphonic acids add step to a) in material calciferous, the amount of adding is 0.05 % by weight to 2.5 % by weight of the gross dry weight based on material calciferous, preferred 0.05 % by weight to 1.5 % by weight, more preferably amount is that 0.05 % by weight to 1 % by weight and most preferred amount are 0.1 % by weight to 1 % by weight.

In a preferred embodiment, carry out step material calciferous a) and step b) the contacting of an alkali metal salt of at least one phosphonic acids, wherein the weight ratio of an alkali metal salt of material calciferous and phosphonic acids is 600:1 to 20:1, more preferably 400:1 to 50:1, even more preferably 300:1 to 100:1 and most preferably 250:1 to 150:1.

Step material calciferous a) can for example, with any suitable form (form of the aqueous solution or drying material) and step b) an alkali metal salt of at least one phosphonic acids mix.The form that an alkali metal salt of at least one phosphonic acids preferably, step b) is the aqueous solution.In a preferred embodiment, the an alkali metal salt of at least one phosphonic acids step b) is the form of the aqueous solution, the an alkali metal salt that it comprises at least one phosphonic acids, 10 % by weight to 80 % by weight that its amount is the gross weight based on solution, preferably 20 % by weight to 66 % by weight and most preferably 30 % by weight to 50 % by weight.

Additionally or alternately, the solids content of suspensoid steps d) obtaining is 50 % by weight to 88 % by weight of the gross weight based on aqueous suspension, preferred 55 % by weight to 88 % by weight, more preferably 65 % by weight to 86 % by weight, even more preferably 68 % by weight to 84 % by weight and most preferably 72 % by weight to 82 % by weight.

The solids content of suspensoid can regulate by method known to the skilled.In order to regulate the solids content of suspensoid calciferous, can be by filtering, centrifugal or thermal separation method partly or entirely dewaters suspensoid.For example, suspensoid can partially or completely dewater as method of evaporating as nanofiltration or thermal separation method by filter method.Alternately, for example can add water to, in the particulate material (being obtained by filtration) of suspensoid calciferous, until obtain the solids content of expectation.Additionally or alternately, can add in the particulate material of aqueous suspension calciferous thering is the suitably suspensoid calciferous of lower solid content, until obtain desired solids content.

In a preferred embodiment of the present invention, regulating step d) obtain the solids content of suspensoid, wherein water is diluted to solids content for 40 % by weight to 90 % by weight of the gross weight based on suspensoid, preferably 50 % by weight to 80 % by weight and more preferably 60 % by weight to 75 % by weight.

An alkali metal salt and the dilute with water of at least one phosphonic acids preferably, interpolation step b) carry out simultaneously.The solids content of the suspensoid for example, regulating step d) obtaining, wherein by step b) the aqueous solution of an alkali metal salt of at least one phosphonic acids add in step material calciferous a).

Preferably under mixing, carry out steps d) contact.

In the methods of the invention, can make step material calciferous a) and step b by any conventional hybrid mode known to the skilled) an alkali metal salt of at least one phosphonic acids mix.

By step b) an alkali metal salt of at least one phosphonic acids to add in step material calciferous a) be not crucial, as long as the pH of gained suspensoid is 10 to 14.Therefore, step b) an alkali metal salt of at least one phosphonic acids of described interpolation can once carry out or carry out with some parts.If by step b) an alkali metal salt of at least one phosphonic acids add in step material calciferous a) and carry out with some parts, described part can comprise the step b of equivalent) an alkali metal salt of at least one phosphonic acids.Alternately, described part can comprise the step b of inequality) an alkali metal salt of at least one phosphonic acids.

Additionally outer or alternately, if by step b) an alkali metal salt of at least one phosphonic acids add in step material calciferous a) and carry out with some parts, be preferably so that the pH of suspensoid can stablize after adding a part and before interpolation next section.

The brookfield viscosity of the aqueous suspension calciferous steps d) obtaining is at 23 ℃, to be 50mPas to 5000mPas, at 23 ℃, be preferably 60mPas to 3000mPas, at 23 ℃, be more preferably 100mPas to 1000mPas and most preferably at 23 ℃ for 50mPas to 900mPas.

According to the present invention, brookfield viscosity passes through to use the Brookfield DVII+ of RVT model after stirring 1 minute ^tMviscometer utilizes suitable N ° of 1 to 5 rotating the needle to measure under the rotating speed of the temperature of approximately 23 ℃ and 100rpm (rotations per minute).

step e): gained suspensoid is contacted with at least one phosphonic acids

According to the step e of the inventive method), make steps d) suspensoid and step c) at least one phosphonic acids contact.Carry out described contact so that acquisition pH is 8 to 10 suspensoid.

The pH of the aqueous suspension calciferous step e in a preferred embodiment of the invention) obtaining is 9 to 10 and preferably approximately 9.4.

Should be understood that selective basis step c of the present invention) the amount of at least one phosphonic acids, make it in steps d) after be enough in the material calciferous that provides, i.e. step e) the pH of suspensoid calciferous be 8 to 10.

In order to obtain step e) pH be 8 to 10 suspensoid calciferous, by step c) at least one phosphonic acids add steps d to) in the suspensoid that obtains, the amount of interpolation is 0.001 % by weight to 0.5 % by weight of the gross dry weight based on material calciferous.

For example, by step c) at least one phosphonic acids add steps d to) in the suspensoid that obtains, the amount of adding is 0.01 % by weight to 0.5 % by weight of the gross dry weight based on material calciferous, preferred 0.05 % by weight to 0.4 % by weight, more preferably amount is that 0.075 % by weight to 0.3 % by weight and most preferred amount are 0.075 % by weight to 0.2 % by weight.

In a preferred embodiment, carry out steps d) suspensoid calciferous and step c) the contacting of at least one phosphonic acids, in wherein said suspensoid, the weight ratio of material calciferous and phosphonic acids is 5000:1 to 200:1, more preferably 4000:1 to 400:1, even more preferably 3000:1 to 500:1 and most preferably 2000:1 to 750:1.

Steps d) suspensoid calciferous obtaining can with the step c of any appropriate form (for example form of the aqueous solution or drying material)) at least one phosphonic acids mix.Preferably, the form that at least one phosphonic acids step c) is the aqueous solution.In a preferred embodiment, step c) at least one phosphonic acids is aqueous solution form, it comprises at least one phosphonic acids, 25 % by weight to 75 % by weight that its amount is the gross weight based on solution, preferably 35 % by weight to 65 % by weight and most preferably 45 % by weight to 60 % by weight.

Additionally or alternately, the solids content of suspensoid step e) obtaining is preferably 50 % by weight to 85 % by weight of the gross weight based on suspensoid, preferred 55 % by weight to 60 % by weight, more preferably 65 % by weight to 80 % by weight, even more preferably 68 % by weight to 78 % by weight and most preferably 68 % by weight to 75 % by weight.

Preferably under mixing, carry out step e) contact.

In the methods of the invention, can make steps d by any conventional hybrid mode known to the skilled) suspensoid calciferous and step c that obtain) at least one phosphonic acids mix.

By step c) at least one phosphonic acids add steps d to) be not crucial in the suspensoid calciferous that obtains, as long as the pH of gained suspensoid is 8 to 10.Therefore, described interpolation can with once or some parts carry out.If by step c) at least one phosphonic acids add steps d to) suspensoid calciferous that obtains carries out with some parts, the step c that described part comprises equivalent) and at least one phosphonic acids.Alternately, described part can comprise the step c of inequality) at least one phosphonic acids.

Additionally or alternately, if by step c) at least one phosphonic acids add steps d to) suspensoid calciferous that obtains carries out with some parts, preferably makes the pH of suspensoid can stablize after adding a part and before interpolation next section.

The brookfield viscosity of the aqueous suspension calciferous step e) obtaining is preferably 10mPas to 4900mPas at 23 ℃, at 23 ℃, be preferably 40mPas to 3000mPas, at 23 ℃, be more preferably 70mPas to 1000mPas and most preferably at 23 ℃ for 100mPas to 800mPas.

According to the present invention, brookfield viscosity is by using the Brookfield DVII+ of RVT model after stirring 1 minute ^tMviscometer is under the rotating speed of the temperature of approximately 23 ℃ and 100rpm (rotations per minute) and utilize suitable N ° of 1 to No. 5 rotating the needle to measure.

step f): optionally grind gained suspensoid

According to the optional step f of the inventive method), grinding steps e) suspensoid.

Grinding steps can be undertaken by the known technology for wet grinding of those skilled in the art and shredder.Grinding steps can carry out with the milling apparatus of any routine, for example, refinement is mainly carried out under the condition from the impact of auxiliary body, in one or more in ball mill, rod mill, oscillating mill, centrifugal impact mill, vertical ball mill, masher or other this equipment known to the skilled, carried out.Grinding steps f) can batch or carry out continuously, preferably carry out continuously.

In a preferred embodiment of the invention, by grinding steps e) suspensoid calciferous.Therefore grinding, step f) is preferably at step e) carry out afterwards.

The pH of suspensoid calciferous preferably, step e to be ground) is 8 to 10, preferably 9 to 10 and more preferably from about 9.4.

The pH of the suspensoid calciferous additionally or alternately, obtaining after grinding is 8 to 10 and preferably 9 to 10.

In a preferred embodiment of the invention, grinding steps f) at 10 ℃ to 110 ℃, preferably 20 ℃ to 90 ℃ and most preferably at the temperature of 20 ℃ to 70 ℃, carry out.

In a preferred embodiment of the invention, carry out grinding steps f) until particle diameter is less than 50 % by weight to 98 % by weight that the part of the material calciferous of 2 μ m is the gross weight based on material calciferous, preferred 60 % by weight to 98 % by weight, more preferably 70 % by weight to 98 % by weight and most preferably 75 % by weight to 98 % by weight, as measured by Sedigraph 5120.

Additionally or alternately, carry out grinding steps f) until being less than the part of the material calciferous of 2 μ m, particle diameter is greater than 50 % by weight for gross weight based on material calciferous, be preferably greater than 60 % by weight, more preferably greater than 70 % by weight, more preferably greater than 75 % by weight and 80 % by weight most preferably from about, as measured by Sedigraph 5120.

The weight median particle d that the suspensoid of the material calciferous additionally or alternately, the step f of the inventive method) obtaining is measured according to sedimentation method ₅₀can be at 0.01 μ m to 10 μ m, preferably 0.1 μ m to 7 μ m and most preferably 0.1 μ m to 5 μ m, for example, in the scope of 0.1 μ m to 4 μ m.

In a preferred embodiment of the invention, the solids content of gained suspensoid step f) is at least 20 % by weight of the gross weight based on suspensoid, preferred 20 % by weight to 90 % by weight, more preferably 30 % by weight to 88 % by weight, even more preferably 40 % by weight to 86 % by weight and most preferably 50 % by weight to 84 % by weight.The solids content of gained suspensoid for example, step f) is 65 % by weight to 82 % by weight or 68 % by weight to 80 % by weight based on the total weight of suspensoid.

The brookfield viscosity of the aqueous suspension calciferous step f) obtaining is preferably in the scope of 1mPas to 5000mPas at 23 ℃, at 23 ℃, be preferably in the scope of 10mPas to 4000mPas, be more preferably in the scope of 20mPas to 3000mPas and most preferably at 23 ℃ in the scope for 30mPas to 1000mPas at 23 ℃.

In a preferred embodiment of the invention, described method also comprises the step g of the suspensoid calciferous of concentrated gained).

In a preferred embodiment of the invention, at step f) before or after carry out enrichment step g).

For example,, at step f) carry out before enrichment step g).Alternately, at step f) carry out afterwards enrichment step g).Preferably, at step f) carry out afterwards enrichment step g).

If implementation step g in the methods of the invention), regulate the solids content in gained suspensoid, make at least 60 % by weight that its amount is the gross weight based on suspensoid, preferred 60 % by weight to 88 % by weight, more preferably 65 % by weight to 86 % by weight, even more preferably 70 % by weight to 84 % by weight and most preferably 75 % by weight to 82 % by weight.

The solids content of gained suspensoid can regulate by concentration method known to the skilled.The concentrated of corresponding suspensoid calciferous can complete by thermal means, for example, in vaporizer or by mechanical means, for example, in pressure filter and/or whizzer, complete.

In a preferred embodiment of the invention, described method comprises the step g of the suspensoid calciferous of concentrated gained), make at least 60 % by weight that the solids content in gained suspensoid is the gross weight based on suspensoid, more preferably at least 65 % by weight and most preferably at least 70 % by weight.For example, described method comprises the step g of the suspensoid calciferous of concentrated gained), make at least 75 % by weight that the solids content in gained suspensoid is the gross weight based on suspensoid, for example 75 % by weight to 82 % by weight.

In a preferred embodiment of the invention, described method comprises the step g of the suspensoid calciferous of concentrated gained), make to obtain desciccate.

Should understand term " desciccate " and refer to such material calciferous, its total surface moisture content, for the gross weight based on material calciferous is less than 0.5 % by weight, is preferably less than 0.2 % by weight and is more preferably less than 0.1 % by weight.

If the inventive method also comprises the step g of the suspensoid calciferous of concentrated gained), make to obtain such desciccate or suspensoid, its solids content is at least 60 % by weight of the gross weight based on suspensoid calciferous, and this desciccate or suspensoid can redilution.If by desciccate or suspensoid redilution, regulate the solids content in gained suspensoid, making it is at least 1 % by weight of the gross weight based on suspensoid, preferred 1 % by weight to 88 % by weight, more preferably 5 % by weight to 86 % by weight, even more preferably 10 % by weight to 84 % by weight and most preferably 15 % by weight to 82 % by weight.

In a preferred embodiment of the invention, described method also comprises step h), it makes step f) and/or step g) suspensoid that comprises material calciferous that obtains contacts with water glass and/or sodium hydroxide.

Preferably, described method also comprises step h), it makes step f) suspensoid that comprises material calciferous that obtains contacts with water glass and/or sodium hydroxide.Alternately, described method also comprises step h), it makes step g) suspensoid that comprises material calciferous that obtains contacts with water glass and/or sodium hydroxide.

Preferably, making step g) suspensoid calciferous that obtains contacts with water glass.Alternately, making step g) suspensoid calciferous that obtains contacts with sodium hydroxide.

In a preferred embodiment of the invention, carry out step h) contact, wherein add water glass and/or sodium hydroxide to step f) and/or step g) in the suspensoid calciferous that obtains, preferably add step g to) in the suspensoid calciferous that obtains, 0.001 % by weight that is greater than that the amount of adding is the gross dry weight based on material calciferous, preferred 0.01 % by weight to 10 % by weight, more preferably 0.05 % by weight to 5 % by weight and most preferably 0.1 % by weight to 4 % by weight.

If methods && steps of implementation h in the methods of the invention), the preferred pH of suspensoid calciferous of gained is greater than 9.5.In a preferred embodiment of the invention, the pH of the suspensoid calciferous of gained is 9.5 to 14.

In view of as the very good result of the above method for the preparation of aqueous suspension calciferous limiting, another aspect of the present invention relates to the suspensoid that comprises material calciferous, and it can obtain by the method according to this invention.This suspensoid comprises highly filled calcium carbonate material, and preferably not containing latex based adhesive.In addition, this suspensoid to be characterized as rheological stable over time, and it is stable over time to be preferably characterized as under water glass and/or sodium hydroxide exist rheological.For example, within 24 hours after suspensoid contacts with water glass and/or sodium hydroxide, measure, the brookfield viscosity of the suspensoid calciferous obtaining by the inventive method is lower than 2500mPas at 23 ℃.Preferably, within 24 hours after suspensoid contacts with water glass and/or sodium hydroxide, measure, the brookfield viscosity of the suspensoid calciferous obtaining by the inventive method at 23 ℃ lower than 2000mPas, more preferably at 23 ℃ lower than 1500mPas and most preferably at 23 ℃ lower than 1000mPas.

According to a further aspect of the present invention, provide the material calciferous that can obtain by dry suspensoid.

Find that gained suspensoid or desciccate can be applicable to paper, paper coating, plastics and/or application of paints.Preferably, find that gained suspensoid or desciccate can be applicable to paper coating application.

In addition, gained suspensoid can be for stablizing the rheological for the coating formulation of paper application, and wherein coating formulation comprises water glass and/or sodium hydroxide.

Should be understood that the above favourable embodiment of describing for the preparation of the method for aqueous suspension calciferous about the present invention also can be used for preparation or limits suspensoid of the present invention, material calciferous and uses thereof.In other words, the arbitrary combination of above-mentioned preferred embodiment and these embodiments is also applicable to suspensoid of the present invention, material calciferous and uses thereof.

Based on following examples, will understand better scope of the present invention and interests, described embodiment is intended to illustrate particular of the present invention and is nonrestrictive.

Embodiment

method and material

Material and measuring method used in embodiment have hereinafter been described.

The solids content of aqueous suspension

The solids content of suspensoid (being also referred to as " dry weight ") is used water analysis device HR73 (from the Mettler-Toledo company of Switzerland) to measure, it is set as: 120 ℃ of temperature, automatic shutdown (automatic switch off) 3, standard is dry, 5 to 20 grams of suspensoids.

The pH of aqueous suspension or solution

The pH of aqueous suspension or solution is used standard pH-meter to measure under the room temperature of approximately 22 ℃.

The size distribution of particulate material (the quality % particle with diameter <X) and weight median particle (d ₅₀)

The weight median particle of particulate material and particle diameter mass distribution are measured via sedimentation method (i.e. the analysis of the sedimentation behavior in gravity field).Measure and use Sedigraph ^tM5120 carry out.

The method and equipment are known to the skilled and are often used to measure the particle diameter of filler and pigment.Measurement is at 0.1 % by weight Na ₄p ₂o ₇the aqueous solution in carry out.Use high speed agitator and supersound process by sample dispersion.

Brookfield viscosity

Brookfield viscosity passes through to use the Brookfield DVII+ of RVT model after stirring 1 minute ^tMviscometer is under the rotating speed of the temperature of approximately 23 ℃ and 100rpm (rotations per minute) and utilize suitable N ° of 1 to No. 5 rotating the needle to measure.

material

Hydrocarb 75ME (suspensoid form, its solids content is 78 % by weight of the gross weight based on suspensoid) is the commercially available calcium carbonate from Omya.This calcium carbonate disperses with polyacrylate.

The Omyacarb 10AV of powder type (solids content is 98 % by weight) is obtained from Omya.The weight median particle d of Omyacarb 10AV ₅₀value is 10 μ m, top minute (top cut) d ₉₈be 50 μ m and d ₂₁value is 2 μ m.

The Omyacarb 2AV of powder type (solids content is 98 % by weight) is obtained from Omya.The weight median particle d of Omyacarb 2AV ₅₀value is 2.6 μ m, top minute d ₉₈be 15 μ m and d ₃₈value is 2 μ m.

CaCO from Molde (Norway) ₃(be called CaCO herein ₃molde) be cake form, solids content is 83 % by weight based on filter cake gross weight, is obtained from Omya.CaCO ₃the weight median particle d of Molde ₅₀value is 7 μ m, top minute d ₉₈be 50 μ m and weight median particle d ₂₃value is 2 μ m.

CaCO from Molde (Norway) ₃slurry (is called CaCO herein ₃molde SL) be suspensoid form, solids content is 74 % by weight based on filter cake gross weight, is obtained from Omya.CaCO ₃the weight median particle d of Molde ₅₀value is 7 μ m, top minute d ₉₈be 50 μ m and weight median particle d ₂₃value is 2 μ m.Its polyacrylic ester with 1000ppm disperses.

The sodium hydroxide of particle form (NaOH) is obtained from Fluka.

Press 1-hydroxyl ethane-1 of the aqueous solution form of dry weight basis 56%, 1-di 2 ethylhexyl phosphonic acid (HEDP) is obtained from Chemische Fabrik Budenheim.

Press (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid four sodium (Na of the aqueous solution form of dry weight basis 32% ₄hEDP) be obtained from Thermophos.

(1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid four potassium (K ₄hEDP) by 90 grams of KOH being added in the HEDP aqueous solution that previously under agitation 200 grams of water is added to 108 gram of 60 % by weight, in the formed HEDP aqueous solution, synthesize.The pH of gained settled solution be 12 and concentration be 33.5 grams of K ₄hEDP/100 gram of water.

Water glass is obtained from PQ Corporation, and trade mark is called Crystall 0075.

Embodiment 1 (inventive embodiments)

This embodiment has illustrated the method for the present invention for the preparation of aqueous suspension calciferous.

Water is by the CaCO of 5.42kg ₃molde is diluted to solids content for 74 % by weight based on suspensoid gross weight.By 0.6 % by weight Na ₄hEDP (based on material gross dry weight calciferous) adds in diluted suspensoid calciferous with form and the 83g water of the 32 % by weight aqueous solution (based on total solution weight).Use is equipped with the dissolving agitator of saw disc agitating plate (saw disk stirring plate) (100 millimeters) under 4000rpm, to make the suspensoid calciferous of gained mix.The solids content of the suspensoid calciferous of gained is 72 % by weight based on suspensoid gross weight.After mixing 30 minutes, value and pH that the brookfield viscosity under 100rpm is shown as 280mPas are 11.1.

Then, by adding the HEDP aqueous solution based on total solution weight 56 % by weight by the pH regulator to 9.4 of suspensoid calciferous, and suspensoid is stirred other 10 minutes.The brookfield viscosity of gained suspensoid under 100rpm is 130mPas, and solids content is 72 % by weight based on suspensoid gross weight.

Subsequently, the suspensoid calciferous that grinds gained is until the weight median particle d of material calciferous ₇₅value is 2 μ m, grinds approximately 60 minutes.For grinding, under about room temperature, use the Dynomill Multilab from W.Bachofen AG to carry out, it is filled with 1070g fusing melting grinding bead, and its soft silica (0.6mm to 1.0mm) by the baddeleyite based on grinding bead gross weight 68 % by weight (baddeleyit) and 32 % by weight forms.The cumulative volume of grinding chamber is 600cm ³.Grinding rate is set as 2500rpm and flow set is 500cm ³min ^-1.

The suspensoid obtaining after grinding is concentrated into solids content for 77.1 % by weight based on suspensoid gross weight in thermal evaporation with under stirring.The pH of gained suspensoid be 9.7 and 100rpm under brookfield viscosity be 160mPas.

Embodiment 2

The prior art suspensoid being disperseed by the salt of polyacrylic ester than calcium carbonate wherein, this embodiment relates to the suspensoid calciferous of preparing by the inventive method is contacted with water glass.

embodiment 2a (comparative example)

In this embodiment, show the suspensoid calciferous of prior art and contacting of water glass.

Water is diluted to by Hydrocarb 75ME – 78% 68 % by weight that solids content is based upon suspensoid gross weight.Under agitation add the water glass of gross dry weight 3 % by weight based on material calciferous.Under 100rpm, measure the brookfield viscosity of gained suspensoid and sample is stored in the airtight beaker of 40 ℃ to 4 hours.After 4 hours, sample is stirred 2 minutes, and under 100rpm, measure the brookfield viscosity of suspensoid.Again sample is stored in the airtight beaker of 40 ℃ to other 20 hours.After total time to 24 hour, sample is stirred 2 minutes and again measures to the brookfield viscosity of suspensoid under 100rpm.

About suspensoid subsequently, through water glass, process and the details of brookfield viscosity after 4 hours and 24 hours is summarized in table 1 respectively.

embodiment 2b (embodiment of the present invention)

In this embodiment, show contacting of water glass and suspensoid calciferous prepared according to the methods of the invention.

Water is diluted to solids content for 68 % by weight based on suspensoid gross weight by the suspensoid obtaining in embodiment 1, under agitation adds the water glass of gross dry weight 3 % by weight based on material calciferous.Under 100rpm, measure the brookfield viscosity of suspensoid and sample is stored in the airtight beaker of 40 ℃ and keep 4 hours.After 4 hours, sample is stirred 2 minutes, and under 100rpm, measure the brookfield viscosity of suspensoid.Again sample is stored in the airtight beaker of 40 ℃ to other 20 hours.After total time to 24 hour, sample is stirred 2 minutes and again measures to the brookfield viscosity of suspensoid under 100rpm.

Table 1:

Upper table 1 illustrates, suspensoid prepared according to the methods of the invention (embodiment 2b) has not only caused suspensoid to contact after 4 hours the brookfield viscosity obviously reducing with water glass, and has caused brookfield viscosity that after 24 hours, brookfield viscosity is measured with prior art suspensoid calciferous (embodiment 2a) to compare reduction being greater than 45%.

Embodiment 3

This embodiment relates to than wherein calcium carbonate is by the prior art suspensoid of the salt dispersion of polyacrylic ester, and the suspensoid calciferous of preparing by the inventive method contacts with sodium hydroxide.

embodiment 3a (comparative example)

In this embodiment, show the suspensoid calciferous of prior art and contacting of sodium hydroxide.

Water is diluted to solids content for 68 % by weight based on suspensoid gross weight by Hydrocarb 75ME-78%, under agitation adds respectively the 1M sodium hydroxide solution of gross dry weight 0.3 % by weight, 0.6 % by weight and 0.9 % by weight based on material calciferous.Under 100rpm, measure the brookfield viscosity of gained suspensoid and each sample is stored in the airtight beaker of 40 ℃ and keep 4 hours.After 4 hours, each sample is stirred 2 minutes, and under 100rpm, measure the brookfield viscosity of each suspensoid.Again each sample is stored in the airtight beaker of 40 ℃ and keeps 20 hours.After total time to 24 hour, each sample is stirred 2 minutes and again measures to the brookfield viscosity of suspensoid under 100rpm.

About suspensoid subsequently through sodium-hydroxide treatment and respectively the details of the brookfield viscosity after 4 hours and 24 hours be summarized in table 2 respectively.

embodiment 3b (embodiment of the present invention)

In this embodiment, showing sodium hydroxide contacts with suspensoid calciferous prepared according to the methods of the invention.

Water is diluted to solids content for 68 % by weight based on suspensoid gross weight by the suspensoid obtaining in embodiment 1, under agitation adds respectively the 1M sodium hydroxide solution of gross dry weight 0.3 % by weight, 0.6 % by weight and 0.9 % by weight based on material calciferous.Under 100rpm, measure the brookfield viscosity of gained suspensoid and each sample is stored in the airtight beaker of 40 ℃ and keep 4 hours.After 4 hours, each sample is stirred 2 minutes, and under 100rpm, measure the brookfield viscosity of suspensoid.Again each sample is stored in the airtight beaker of 40 ℃ and keeps 20 hours.After total time to 24 hour, each sample is stirred 2 minutes and again measures to the brookfield viscosity of suspensoid under 100rpm.

About suspensoid subsequently, through the details of sodium-hydroxide treatment and the brookfield viscosity after 4 hours and 24 hours, be summarized in table 2 respectively.

Table 2:

By table 2 deducibility, gone out, prior art suspensoid calciferous (embodiment 3a) causes brookfield viscosity obviously to increase in time with contacting of sodium hydroxide.Or rather, can be observed the initial brookfield viscosity of directly measuring after contacting with sodium hydroxide with respect to suspensoid, the brookfield viscosity of the suspensoid contacting with 0.6 % by weight with 0.3 % by weight has respectively increased more than 100% in 24 hours.About the suspensoid contacting with 0.9 % by weight sodium hydroxide, deducibility goes out with respect to suspensoid, to contact the rear initial brookfield viscosity of directly measuring with sodium hydroxide, and brookfield viscosity has increased more than 80% in 24 hours.

With its by contrast, table 2 also illustrates suspensoid calciferous prepared according to the methods of the invention obviously to be reduced with the initial brookfield viscosity of directly having measured after (embodiment 3b) not only caused suspensoid to contact with sodium hydroxide that contacts of sodium hydroxide, and has caused brookfield viscosity stable in time.

Embodiment 4

This embodiment relates to by using the K of different amounts ₄hEDP and HEDP prepare aqueous suspension calciferous.

With 258g water dilution 2.5kg CaCO ₃molde.Respectively by the K of 0.2 % by weight, 0.4 % by weight and 0.6 % by weight ₄hEDP (gross dry weight based on material calciferous) adds in diluted suspensoid calciferous with the form of the 42 % by weight aqueous solution (based on total solution weight).Use is equipped with the dissolving agitator of saw disc agitating plate (100 millimeters) under 4000rpm, gained suspensoid to be mixed.The solids content of each gained suspensoid is 75.3 % by weight based on suspensoid gross weight.Mix after 30 minutes, value and pH that the brookfield viscosity of 100rpm low suspension body is shown as respectively 247mPas, 425mPas and 467mPas are respectively 10.7,11.2 and 11.3.

Then, the K of 0.6 % by weight will be passed through to add ₄suspensoid prepared by HEDP (based on material gross dry weight calciferous), the HEDP (gross dry weight based on material calciferous) of 0.15 % by weight of form (based on total solution weight) by adding the 30 % by weight aqueous solution be pH regulator to 9.4, and suspensoid is stirred other 10 minutes.Under 100rpm, the brookfield viscosity of gained suspensoid is 110mPas, and solids content is 75.3 % by weight based on suspensoid gross weight.

Subsequently, grind this suspensoid until the weight median particle d of material calciferous ₇₆value is 2 μ m.For grinding, under about room temperature, use the DynomillMultilab from W.Bachofen AG to carry out, it is filled with 1070g fusing melting grinding bead, and its soft silica by the baddeleyite based on grinding bead gross weight 68 % by weight and 32 % by weight (0.6 millimeter to 1.0 millimeters) forms.The cumulative volume of grinding chamber is 600cm ³.Grinding rate is set as 2500rpm and flow set is 500cm ³min ^-1.

After grinding the pH of gained suspensoid be 9.6 and the brookfield viscosity under 100rpm be 230mPas.

About calcium carbonate suspensoid and the K that adds ₄the details of the brookfield viscosity of HEDP and HEDP and pH, solids content, corresponding suspensoid is summarized in table 3.

Table 3:

* CaCO ₃from Molde

By table 3 deducibility, go out to increase K ₄the interpolation of HEDP causes brookfield viscosity to increase.Yet, and deducibility goes out follow-up interpolation HEDP and causes brookfield viscosity obviously to reduce.

Embodiment 5

This embodiment relates to the Na that uses different amounts ₄hEDP and HEDP prepare aqueous suspension calciferous.

With 225g water dilution 2.1kg CaCO ₃molde.Respectively by the Na of 0.2 % by weight of the gross dry weight based on material calciferous, 0.4 % by weight and 0.6 % by weight based on total solution weight 20 % by weight aqueous solution forms ₄hEDP adds in diluted suspensoid calciferous.Use is equipped with the dissolving agitator of saw disc agitating plate (100 millimeters) under 4000rpm, gained suspensoid to be mixed.The solids content of gained suspensoid is respectively 75.6 % by weight, 75.1 % by weight and 75.0 % by weight based on suspensoid gross weight.After mixing 30 minutes, value and pH that the brookfield viscosity of 100rpm low suspension body is shown as respectively 440mPas, 670mPas and 690mPas are respectively 10.8,11.1 and 11.2.

Then, the K of 0.6 % by weight will be passed through to add ₄suspensoid prepared by HEDP (based on material gross dry weight calciferous), the HEDP (gross dry weight based on material calciferous) of 0.15 % by weight of form (based on total solution weight) by adding the 28 % by weight aqueous solution be pH regulator to 9.4, and suspensoid is stirred other 10 minutes.Under 100rpm, the brookfield viscosity of gained suspensoid is 390mPas, and solids content is 74.9 % by weight based on suspensoid gross weight.

Subsequently, grind this suspensoid until the weight median particle d of material calciferous ₇₇value is 2 μ m.For grinding, under about room temperature, use the Dynomill Multilab from W.Bachofen AG to carry out, it is filled with 1070g fusing melting grinding bead, and its soft silica by the baddeleyite based on grinding bead gross weight 68 % by weight and 32 % by weight (0.6 millimeter to 1.0 millimeters) forms.The cumulative volume of grinding chamber is 600cm ³.Grinding rate is set as 2500rpm and flow set is 500cm ³min ^-1.

After grinding gained suspensoid pH be 9.6 and the brookfield viscosity under 100rpm be 180mPas.

After grinding, gained suspensoid is further concentrated into solids content for 77.9 % by weight based on suspensoid gross weight by thermal evaporation and stirring.The pH of gained suspensoid be 9.6 and the brookfield viscosity under 100rpm be 180mPas.

About calcium carbonate suspensoid and the Na adding ₄the details of the brookfield viscosity of HEDP and HEDP and pH, solids content, corresponding suspensoid is summarized in table 4.

Table 4:

* CaCO ₃from Molde

By table 4 deducibility, gone out, HEDP sylvite is disperseing to comprise the CaCO from Molde ₃to seem efficiency slightly high the material aspect of calcium carbonate.The brookfield viscosity of the suspensoid that the HEDP sodium salt that is 75 % by weight with solids content contacts is higher than the suspensoid viscosity contacting with HEDP sylvite (reference example 4).

Embodiment 6

This embodiment relates to use Omyacarb 10AV in conjunction with Na ₄hEDP and HEDP prepare aqueous suspension calciferous.

889g water is placed in to 5 liters of buckets and under agitation adds 60g Na ₄hEDP.Use is equipped with the dissolving agitator of saw disc agitating plate (100 millimeters) under agitation 2.55kg Omyacarb 10AV progressively to be added in this solution under 4000rpm.The solids content of gained suspensoid is 72.2 % by weight based on suspensoid gross weight.Mix after 30 minutes, value and pH that the brookfield viscosity of the suspensoid under 100rpm is shown as 400mPas are 11.0.

Then, the HEDP by adding 0.15 % by weight of the gross dry weight based on material calciferous based on total solution weight 28 % by weight aqueous solution forms is the pH regulator to 9.4 of suspensoid, and suspensoid is stirred other 10 minutes.The brookfield viscosity of gained suspensoid is 160mPas under 100rpm, and solids content is 72.2 % by weight based on suspensoid gross weight.

Subsequently, grind this suspensoid until the weight median particle d of material calciferous ₇₆value is 2 μ m.For grinding, under about room temperature, use the Dynomill Multilab from W.Bachofen AG to carry out, it is filled with 1070g fusing melting grinding bead, and its soft silica by the baddeleyite based on grinding bead gross weight 68 % by weight and 32 % by weight (0.6 millimeter to 1.0 millimeters) forms.The cumulative volume that grinding chamber has is 600cm ³.Grinding rate is set as 2500rpm and flow set is 500cm ³min ^-1.

After grinding the pH of gained suspensoid be 9.7 and the brookfield viscosity under 100rpm be 110mPas.

After grinding, gained suspensoid is further concentrated into solids content for 77.9 % by weight based on suspensoid gross weight by thermal evaporation and stirring.The pH of gained suspensoid be 9.6 and the brookfield viscosity under 100rpm be 160mPas.

About calcium carbonate suspensoid and the Na adding ₄the details of the brookfield viscosity of HEDP and HEDP and pH, solids content, corresponding suspensoid is summarized in table 5.

Table 5:

By table 5 deducibility, go out brookfield viscosity still stable after 7 days.

Embodiment 7

This embodiment relates to use Omyacarb 2AV in conjunction with Na ₄hEDP and HEDP prepare aqueous suspension calciferous.

361g water is placed in to 5 liters of buckets and under agitation adds 17g Na ₄hEDP.Use is equipped with the dissolving agitator of saw disc agitating plate (100 millimeters) under agitation 1.02kg Omyacarb 2AV progressively to be added in this solution under 4000rpm.The solid topic content of gained suspensoid is 72.2 % by weight based on suspensoid gross weight.Mix after 30 minutes, value and pH that the brookfield viscosity of the suspensoid under 100rpm is shown as 585mPas are 10.8.

Then, the HEDP by adding 0.15 % by weight of the gross dry weight based on material calciferous based on total solution weight 28 % by weight aqueous solution forms is the pH regulator to 9.4 of suspensoid, and suspensoid is stirred other 10 minutes.The brookfield viscosity of gained suspensoid is 380mPas under 100rpm, and solids content is 72.0 % by weight based on suspensoid gross weight.

Then, grind this suspensoid until the weight median particle d of material calciferous ₈₀value is 2 μ m.For grinding, under about room temperature, use the Dynomill Multilab from W.Bachofen AG to carry out, it is filled with 1070g fusing melting grinding bead, and its soft silica by the baddeleyite based on grinding bead gross weight 68 % by weight and 32 % by weight (0.6 millimeter to 1.0 millimeters) forms.The cumulative volume of grinding chamber is 600cm ³.Grinding rate is set as 2500rpm and flow set is 500cm ³min ^-1.

After grinding the pH of gained suspensoid be 9.7 and the brookfield viscosity under 100rpm be 180mP _as.

Details about grinding condition is summarized in table 6.

Table 6:

T[minute]	T[℃]	P[bar]	Explain
				0	22	0	Initial → cascade
7:00	42	0.3–0.4	First stage completes → circulates
				10:00	44	0.3–0.4	Stop 2 μ m < 61% → continue
17:00	42	0.4–0.5	Stop 2 μ m < 66% → continue
				25:00	42	0.4–0.5	Final 2 μ m < 80%

After grinding, gained suspensoid is further concentrated into solids content for 77.7 % by weight based on suspensoid gross weight by thermal evaporation and stirring.The pH of gained suspensoid be 9.5 and the brookfield viscosity under 100rpm be 440mPas.

About calcium carbonate suspensoid and add and put into Na ₄the details of the brookfield viscosity of HEDP and HEDP and pH, solids content, corresponding first, second and combined suspension body is summarized in table 7.

Table 7:

By table 7 deducibility, go out brookfield viscosity still stable after 7 days.

Embodiment 8 (comparative example)

This embodiment relates to use Omyacarb 10AV in conjunction with Na ₄hEDP prepares water-based suspensoid calciferous, wherein with HEDP, does not regulate pH.

798g water is placed in to 5 liters of buckets and under agitation adds 31g Na ₄hEDP.Use is equipped with the dissolving agitator of saw disc agitating plate (100 millimeters) under agitation 2.17kg Omyacarb 10AV progressively to be added in this solution under 4000rpm.The solids content of gained suspensoid is 72.2 % by weight based on suspensoid gross weight.Mix after 30 minutes, value and pH that the brookfield viscosity of suspensoid is shown as 150mPas under 100rpm are 10.6.

Subsequently, grind this suspensoid until the weight median particle d of material calciferous ₇₄value is 2 μ m.For grinding, under about room temperature, use the Dynomill Multilab from W.Bachofen AG to carry out, it is filled with 1070g and melts still grinding bead, and its soft silica by the baddeleyite based on grinding bead gross weight 68 % by weight and 32 % by weight (0.6 millimeter to 1.0 millimeters) forms.The cumulative volume of grinding chamber is 600cm ³.Grinding rate is set as 2500rpm and flow set is 500cm ³min ^-1.Must stop grinding the slurry retrogradation in shredder and must stop grinding while almost causing shredder total blockage.Therefore, should note the method inapplicable.

After grinding the pH of gained suspensoid be 10.2 and the brookfield viscosity under 100rpm be 310mPas.

Details about grinding condition part is summarized in table 8.

Table 8:

T[minute]	T[℃]	P[bar]	Explain
				0	24	0	Initial → cascade
3:40	36	0.3	First stage completes → circulates
				7:20	37	0.3–0.4	-
11:00	40	0.4–0.5	-
				14:40	40	0.4–0.5	-
19:20	41	0.4–0.5	Stop 2 μ m < 67% → continue
				22:00	42	0.6–0.7	Final 2 μ m < 74% → rolling grinding machine outlet retrogradation

After grinding, gained suspensoid is further concentrated into solids content for 77.0 % by weight based on suspensoid gross weight by thermal evaporation and stirring.The pH of the suspensoid of gained be 10.0 and the brookfield viscosity under 100rpm be 1730mPas.

About calcium carbonate suspensoid and add Na ₄the detailed content of the brookfield viscosity of HEDP and pH, solids content, corresponding suspensoid is summarized in table 9.

Table 9:

By table 9 deducibility, gone out, the suspensoid that contains material calciferous only contacts (further not adding HEDP) and causes brookfield viscosity obviously to increase with an alkali metal salt of HEDP.In addition, it should be noted that, this suspensoid is also not suitable as painting color preparation.In addition, this result demonstrates the favourable character of the aqueous suspension calciferous of preparing by the inventive method.

Embodiment 9 (embodiment of the present invention)

This embodiment has illustrated the possibility of the step of use according to the present invention material calciferous disperseing through polyacrylic ester a) as raw material.

Use is equipped with the dissolving agitator of saw disc agitating plate (100 millimeters) under 4000rpm, to stir 4.0kg CaCO ₃molde SL.Under agitation add 83g water.The solids content of gained suspensoid is 72.3 % by weight based on suspensoid gross weight.The 76.1g Na of interpolation based on total solution weight 32 % by weight aqueous solution forms ₄hEDP solution.Mix after 30 minutes, value and pH that the brookfield viscosity of suspensoid is shown as 920mPas under 100rpm are 11.1.

Subsequently, the HEDP by adding 0.15 % by weight of the gross dry weight based on material calciferous based on total solution weight 56 % by weight aqueous solution forms is the pH regulator to 9.4 of suspensoid, and suspensoid is stirred other 10 minutes.The brookfield viscosity of gained the first suspensoid is 160mPas under 100rpm, and solids content is 71.7 % by weight based on suspensoid gross weight.

Subsequently, grind suspensoid until the weight median particle d of material calciferous ₇₉value is 2 μ m.For grinding, under about room temperature, use the Dynomill Multilab from W.Bachofen AG to carry out, it is filled with 1070g fusing melting grinding bead, and its soft silica by the baddeleyite based on grinding bead gross weight 68 % by weight and 32 % by weight (0.6 millimeter to 1.0 millimeters) forms.The cumulative volume of grinding chamber is 600cm ³.Grinding rate is set as 2500rpm and flow set is 500cm ³min ^-1.Slurry retrogradation in shredder and must stop while almost causing shredder total blockage grinding.Therefore, should note the method inapplicable.

After grinding, gained suspensoid is further concentrated into solids content for 78.1 % by weight based on suspensoid gross weight by thermal evaporation and stirring.The pH of the suspensoid that obtains be 9.7 and the brookfield viscosity under 100rpm be 220mPas.

Claims

1. for the preparation of a method for aqueous suspension calciferous, it comprises the following steps:

A) provide the material calciferous of water-based filter cake or suspensoid form, its solids content is at least 45 % by weight of the gross weight based on described water-based filter cake or suspensoid;

B) with the amount of 0.01 % by weight to 5 % by weight of the gross dry weight based on described material calciferous, provide an alkali metal salt of at least one phosphonic acids;

C) amount with 0.001 % by weight to 0.5 % by weight of the gross dry weight based on described material calciferous provides at least one phosphonic acids;

D) make step material described calciferous a) and step b) an alkali metal salt of described at least one phosphonic acids contact, take and obtain the suspensoid of pH as 10 to 14;

E) make steps d) described suspensoid and step c) described at least one phosphonic acids contact, take and obtain the suspensoid of pH as 8 to 10; And

F) described suspensoid grinding steps e optionally) obtaining.

2. method according to claim 1, wherein step material described calciferous a) is grinding calcium carbonate, precipitated chalk, modified calcium carbonate or its mixture.

3. method according to claim 1 and 2, wherein described filter cake a) of step or the solids content of suspensoid are 50 % by weight to 98 % by weight of the gross weight based on described water-based filter cake or suspensoid, preferably 60 % by weight to 90 % by weight and more preferably 70 % by weight to 85 % by weight.

4. the weight median particle d of step described material calciferous a) wherein according to the method in any one of claims 1 to 3, ₅₀be 1 μ m to 100 μ m, preferred 1 μ m to 70 μ m, more preferably 1 μ m to 50 μ m, even more preferably 1 μ m to 25 μ m and most preferably 1 μ m to 10 μ m.

5. according to the method described in any one in claim 1 to 4, the basic metal of an alkali metal salt of described at least one phosphonic acids step b wherein) is selected from sodium, potassium, lithium and composition thereof, the described basic metal of an alkali metal salt of described at least one phosphonic acids preferably, step b) is sodium.

6. according to the method described in any one in claim 1 to 5, the an alkali metal salt of described at least one phosphonic acids step b wherein) is selected from an alkali metal salt of di 2 ethylhexyl phosphonic acid and an alkali metal salt of tri methylene phosphonic acid, preferably, an alkali metal salt that an alkali metal salt of described at least one phosphonic acids is di 2 ethylhexyl phosphonic acid.

7. according to the method described in any one in claim 1 to 6, the an alkali metal salt that an alkali metal salt of described at least one phosphonic acids step b wherein) is di 2 ethylhexyl phosphonic acid, described di 2 ethylhexyl phosphonic acid is selected from 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid (HEDP), methylenediphosphonate (MDP) (MDP), hydroxy methylene di 2 ethylhexyl phosphonic acid (HMDP), hydroxyl ring methylenediphosphonate (MDP) (HCMDP) and 1-hydroxyl-3-aminopropane-1,1-di 2 ethylhexyl phosphonic acid (APD), preferred 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid (HEDP).

8. an alkali metal salt of described di 2 ethylhexyl phosphonic acid according to the method described in any one in claim 1 to 7, wherein said step b) is selected from (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid four sodium (Na ₄hEDP), (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid trisodium (Na ₃hEDP), (1-hydroxy ethylene) Disodium alendronate (Na ₂hEDP), (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid four potassium (K ₄hEDP), (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid tripotassium (K ₃hEDP) and (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid dipotassium (K ₂an alkali metal salt of described di 2 ethylhexyl phosphonic acid HEDP), preferably, step b) is (1-hydroxy ethylene) di 2 ethylhexyl phosphonic acid four sodium (Na ₄hEDP).

9. according to the method described in any one in claim 1 to 8, the basic metal of described at least one phosphonic acids step b wherein) is aqueous solution form, be preferably the aqueous solution of an alkali metal salt that comprises described at least one phosphonic acids, the amount of an alkali metal salt of described at least one phosphonic acids is 10 % by weight to 80 % by weight of the gross weight based on described solution, preferably 20 % by weight to 66 % by weight and most preferably 30 % by weight to 50 % by weight.

10. described at least one phosphonic acids according to the method described in any one in claim 1 to 9, step c wherein) is selected from di 2 ethylhexyl phosphonic acid and tri methylene phosphonic acid, and preferably, described at least one phosphonic acids is di 2 ethylhexyl phosphonic acid.

11. according to the method described in any one in claim 1 to 10, step c wherein) described at least one phosphonic acids is di 2 ethylhexyl phosphonic acid, it is selected from 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid (HEDP), methylenediphosphonate (MDP) (MDP), hydroxy methylene di 2 ethylhexyl phosphonic acid (HMDP), hydroxyl ring methylenediphosphonate (MDP) (HCMDP) and 1-hydroxyl-3-aminopropane-1,1-di 2 ethylhexyl phosphonic acid (APD), preferably, step c) described at least one phosphonic acids is 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid (HEDP).

12. according to the method described in any one in claim 1 to 11, step c wherein) described at least one phosphonic acids is aqueous solution form, be preferably and comprise described at least one phosphine aqueous acid, the amount of described at least one phosphonic acids is 25 % by weight to 75 % by weight of the gross weight based on described solution, preferably 35 % by weight to 65 % by weight and most preferably 45 % by weight to 60 % by weight.

13. according to the method described in any one in claim 1 to 12, wherein said step b) an alkali metal salt of described at least one phosphonic acids be 1-hydroxyl ethane 1, the sodium salt (Na of 1-di 2 ethylhexyl phosphonic acid ₄hEDP), and step c described at least one phosphonic acids) is 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid (HEDP).

14. according to the method described in any one in claim 1 to 13, wherein carry out steps d), wherein by step b) an alkali metal salt of described at least one phosphonic acids with 0.05 % by weight to 2.5 % by weight of the gross dry weight based on described material calciferous, preferably its amount is 0.05 % by weight to 1.5 % by weight, more preferably its amount be 0.05 % by weight to 1 % by weight and most preferably its amount be that the amount of 0.1 % by weight to 1 % by weight is added in step material described calciferous a).

15. according to the method described in any one in claim 1 to 14, wherein steps d) pH of the described suspensoid that obtains is 9 to 12, preferably 10 to 12 and most preferably from about 11.

16. according to the method described in any one in claim 1 to 15, wherein water is by steps d) the described suspensoid that obtains is diluted to solids content for 40 % by weight to 90 % by weight of the gross weight based on described suspensoid, preferably 50 % by weight to 80 % by weight and more preferably 60 % by weight to 75 % by weight.

17. according to the method described in any one in claim 1 to 16, the solids content of described suspensoid steps d wherein) obtaining is 50 % by weight to 88 % by weight of the gross weight based on described suspensoid, preferred 55 to 88 % by weight, more preferably 65 % by weight to 86 % by weight, even more preferably 68 % by weight to 84 % by weight and most preferably 72 % by weight to 82 % by weight.

18. according to the method described in any one in claim 1 to 17, the brookfield viscosity of described suspensoid steps d wherein) obtaining is 50mPas to 5000mPas at 23 ℃, at 23 ℃, be preferably 60mPas to 3000mPas, at 23 ℃, be more preferably 100mPas to 1000mPas and most preferably at 23 ℃ for 150mPas to 900mPas.

19. according to the method described in any one in claim 1 to 18, wherein carry out step e), wherein by step c) described at least one phosphonic acids with 0.01 % by weight to 0.5 % by weight of the gross dry weight based on described material calciferous, preferably its amount is 0.05 % by weight to 0.4 % by weight, more preferably its amount be 0.075 % by weight to 0.3 % by weight and most preferably its amount be that the amount of 0.075 % by weight to 0.2 % by weight is added steps d to) in the described suspensoid that obtains.

20. according to the method described in any one in claim 1 to 19, wherein step e) pH of the described suspensoid that obtains is 9 to 10 and most preferably from about 9.4.

21. according to the method described in any one in claim 1 to 20, the brookfield viscosity of described suspensoid step e wherein) obtaining is 10mPas to 4900mPas at 23 ℃, at 23 ℃, be preferably 40mPas to 3000mPas, at 23 ℃, be more preferably 70mPas to 1000mPas and most preferably at 23 ℃ for 100mPas to 800mPas.

22. according to the method described in any one in claim 1 to 21, wherein at step e) carry out afterwards grinding steps f).

23. according to the method described in any one in claim 1 to 22, wherein at 10 ℃ to 110 ℃, preferably 20 ℃ to 90 ℃ and most preferably at the temperature of 20 ℃ to 70 ℃, carry out grinding steps f).

24. according to the method described in any one in claim 1 to 23, wherein carry out grinding steps f) until particle diameter is less than 50 % by weight to 98 % by weight that the part of the material calciferous of 2 μ m is the gross weight based on described material calciferous, preferred 60 % by weight to 98 % by weight, more preferably 70 % by weight to 98 % by weight and most preferably 75 % by weight to 98 % by weight.

25. according to the method described in any one in claim 1 to 24, the brookfield viscosity of described suspensoid step f wherein) obtaining at 23 ℃ in the scope of 1mPas to 5000mPas, preferably at 23 ℃ in the scope of 10mPas to 4000mPas, more preferably at 23 ℃ in the scope of 20mPas to 3000mPas and most preferably at 23 ℃ in the scope of 30mPas to 1000mPas.

26. according to the method described in any one in claim 1 to 25, wherein said method also comprises the step g of the suspensoid that comprises material calciferous of concentrated gained), make at least 60 % by weight that the solids content in described suspensoid is the gross weight based on described suspensoid, preferred 60 % by weight to 88 % by weight, more preferably 65 % by weight to 86 % by weight, even more preferably 70 % by weight to 84 % by weight and most preferably 75 % by weight to 82 % by weight.

27. methods according to claim 26, wherein at step f) carry out afterwards enrichment step g).

28. according to the method described in any one in claim 1 to 27, and wherein said method also comprises step h), it makes step f) and/or step g) in gained described in contain material calciferous described suspensoid contact water glass and/or sodium hydroxide.

29. methods according to claim 28, wherein carry out step h) described contact, wherein with the gross dry weight based on described material calciferous, be greater than 0.001 % by weight, preferred 0.01 % by weight to 10 % by weight, more preferably 0.05 % by weight to 5 % by weight and most preferably the amount of 0.1 % by weight to 4 % by weight add water glass and/or sodium hydroxide.

30. 1 kinds of suspensoids, it comprises can be by the material calciferous obtaining according to the method described in any one in claim 1 to 29.

31. 1 kinds of materials calciferous, it can obtain according to the suspensoid described in claim 30 by dry.

32. suspensoids according to claim 30 or the purposes of material calciferous according to claim 31 in paper, paper coating, plastics and/or application of paints.

33. suspensoids according to claim 30 are for stablizing the purposes of the rheological of coating formulation in paper application, wherein said coating formulation comprises water glass and/or sodium hydroxide.